Process for telomerization of butadiene

ABSTRACT

In an improved process for telomerizing butadiene, contact butadiene and an organic hydroxy compound represented by formula ROH (I), wherein R is a substituted or unsubstituted C 1 -C 20 -hydrocarbyl and the organic hydroxy compound is not glycerol, in a reaction fluid in the presence of a palladium catalyst and a phosphine ligand represented by formula PAr 3  (II), wherein each Ar is independently a substituted or unsubstituted aryl having a hydrogen atom on at least one ortho position, at least two Ar groups are ortho-hydrocarbyloxyl substituted aryls. The phosphine ligand has a total of two (2), three (3), four (4), five (5), or six (6) substituted or unsubstituted C 1 -C 20 -hydrocarbyloxyls, and optionally, any two adjacent substituents on an Ar group can be bonded to form a 5- to 7-membered ring.

This application is a non-provisional application claiming priority fromthe U.S. Provisional Patent Application No. 61/088,186, filed on Aug.12, 2008, entitled “AN IMPROVED PROCESS FOR TELOMERIZATION OFBUTADIENE,” the teachings of which are incorporated by reference herein,as if reproduced in full hereinbelow.

The present invention relates generally to a process for telomerizing1,3-butadiene in the presence of an organic hydroxy compound, apalladium catalyst and a phosphine ligand.

Telomerization of 1,3-butadiene, hereinafter simply referred to asbutadiene, in the presence of a nucleophile, such as an alkanol, is aknown reaction for oligomerizing, especially dimerizing, butadiene toproduce commercially useful chemicals having eight or more carbon atoms.The reaction typically produces a mixture comprising primarily a linearproduct, 1-alkoxy-2,7-octadiene, and minor products such as a branched3-alkoxy-1,7-octadiene and 1,3,7-octatriene. The linear product is auseful starting material for producing 1-octene, a co-monomer forproducing plastics. See for example WO92/10450 (Bohley et al.), U.S.Patent Application Publication 2005/0038305 (Edwards) and U.S. Pat. No.7,030,286 (Rottger et al.).

In producing 1-octene from a butadiene telomerization product mixture,the branched product 3-alkoxy-1,7-octadiene leads to production ofundesirable by-products, 2- and 3-octenes, which may need to be removedfrom the desired product 1-octene. Therefore, it is desirable tomaximize a 1-alkoxy-2,7-octadiene to 3-alkoxy-1,7-octadiene molar ratioin the butadiene telomerization product mixture when 1-octene is apreferred final product with little or no, preferably no, 2-octene or3-octene.

The telomerization reaction is generally catalyzed by a ligand complexof a transition metal selected from a group consisting of iron (Fe),cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd),osmium (Os), iridium (Ir) and platinum (Pt). Preferably, the transitionmetal is palladium. Phosphines are examples of ligands that can formefficient palladium catalysts suitable for use in producing1-alkoxy-2,7-octadiene.

U.S. Pat. No. 7,141,539 and U.S. 2005/0038305, both of Edwards, relategenerally to using palladium complexes of certain alkoxy substitutedphosphines (e.g., tris-(2,4,6-trimethoxyphenyl)phosphine andtris-(4-methoxyphenyl)phosphine) as catalysts to promote butadienetelomerization with an alkanol or an α,ω-diol to form a productcomprising primarily 1-alkoxy- or 1-hydroxyalkoxy-substituted octadiene,respectively.

SUMMARY OF THE INVENTION

In some embodiments, this invention provides an improved process fortelomerizing butadiene, the process comprising contacting butadiene andan organic hydroxy compound represented by formula ROH (I), wherein R isa substituted or unsubstituted C₁-C₂₀-hydrocarbyl and the organichydroxy compound is not glycerol, in a reaction fluid in the presence ofa palladium catalyst and a phosphine ligand, the improvement comprising,

a) the phosphine ligand being selected from a group represented byformula (II):

wherein:R¹, R², R³ and R⁴ are each independently selected from a groupconsisting of hydrogen, halogen, substituted and unsubstitutedC₁-C₂₀-hydrocarbyls, and substituted and unsubstitutedC₁-C₂₀-hydrocarbyloxyls, provided that at least two R¹ moieties areindependently selected from substituted or unsubstitutedC₁-C₂₀-hydrocarbyloxyls and that the phosphine ligand has a total of two(2), three (3), four (4), five (5), or six (6) substituted orunsubstituted C₁-C₂₀-hydrocarbyloxyls;wherein optionally on each phenyl ring, R¹ is bonded to R² to form a 5-to 7-membered ring, R² is bonded to R³ to form a 5- to 7-membered ring,or R³ is bonded to R⁴ to form a 5- to 7-membered ring; and

b) which contacting occurs in a reaction fluid that comprises thebutadiene, the organic hydroxy compound, the palladium catalyst and thephosphine ligand under conditions and for a reaction time sufficient toyield a product mixture comprising a linear product 1-RO-2,7-octadieneand a branched product 3-RO-1,7-octadiene with a linear product tobranched product molar ratio of greater than (>) 25/1 and a catalystefficiency at least (≧) 150 grams (g) of the linear product per gpalladium per hour (g/g/hr), wherein R is as defined above.

All percentages, preferred amounts or measurements, ranges and endpointsthereof herein are inclusive, that is, “a range from 5 to 10” includes 5and 10.

A “hydrocarbyl” is a univalent moiety derived from a hydrocarbon byremoval of one hydrogen atom from one carbon atom, which carbon atom isalso defined as an “alpha” carbon or a carbon placed in the alphaposition. A hydrocarbyl can be an alkyl, alkenyl, alkynyl, or aryl, aunivalent moiety derived from an alkane, alkene, alkyne, or arene,respectively, by removal of one hydrogen atom from one carbon atom.

A “hydrocarbylene” is a divalent moiety derived from a hydrocarbon byremoval of two hydrogen atoms from two carbon atoms. A hydrocarbylene,except methylene, has two alpha carbon atoms, each named according toits position in the hydrocarbylene.

A “beta” carbon/position is a carbon atom that is directly bonded to thealpha carbon. A gamma carbon/position is a carbon atom that is directlybonded to a beta carbon and is two bonds away from the alpha carbon.

A “substituted hydrocarbyl” or “substituted hydrocarbylene” means thatone or more hydrogen (H) or carbon (C) atom(s) in the hydrocarbyl or thehydrocarbylene is substituted by one or more heteroatom(s) or one ormore functional group(s) that contain one or more heteroatom(s) such asnitrogen, oxygen, sulfur, phosphorus, boron, fluorine, chlorine,bromine, and iodine.

A “hydrocarbyloxyl” or “substituted hydrocarbyloxyl” is a univalentmoiety having a generic formula of RO—, wherein R is a hydrocarbyl orsubstituted hydrocarbyl, respectively, as defined above. Ahydrocarbyloxyl is an alkoxyl when R is an alkyl, or an aryloxyl when Ris an aryl.

The “pK_(b)” of a base has its ordinary definition of being equal to“−log₁₀K_(b)”, where K_(b) is the dissociation constant of the acidconjugate to the base in water.

Define number of carbon atoms or a range thereof forming a moiety orcompound by prefixing the moiety or compound with a formula “C_(m)—” or“C_(m)—C_(n)—,” respectively, wherein m and n are integers.

Abbreviations and symbols “° C.,” “g,” “L,” “ml,” “mol,” “mmol,” “M,”“mM,” “conv,” “eq,” “psi,” “mPa” and “NMR” are used, respectively, for“degree Celsius,” “gram,” “liter,” “milliliter,” “mole,” “millimole,”“moles/liter,” “millimole/liter,” “conversion,” “equivalent,” “poundsper square inch,” “mega Pascal” and “nuclear magnetic resonance,”respectively, and plural forms thereof.

In some embodiments, this invention provides a process that comprisescontacting butadiene with an organic hydroxy compound of formula ROH (I)in the presence of a palladium catalyst and a phosphine ligandrepresented by formula (II):

wherein the organic hydroxy compound and R¹ through R⁴ are as definedabove.

Contacting occurs in a reaction fluid that comprises the butadiene, theorganic hydroxy compound, the palladium catalyst, and the phosphineligand. The reaction fluid may further comprise one or more optionalcomponent(s), such as an organic solvent, a catalyst promoter, acatalyst stabilizer, or a butadiene polymerization inhibitor, whichoptional components will be described in more detail hereinbelow.

The above phosphine ligand advantageously has ≧two aryls each of whichis substituted by one C₁-C₂₀-hydrocarbyloxyl substituent on only one ofits ortho positions.

Examples of suitable phosphines include, but are not limited to,tris-(2-methoxyphenyl)phosphine, tris-(2-ethoxyphenyl)phosphine,tris-(2-propoxyphenyl)phosphine, tris-(2-i-propoxyphenyl)phosphine,tris-(2-butoxyphenyl)phosphine, tris-(2-sec-butoxyphenyl)phosphine,tris-(2-t-butoxyphenyl)phosphine, tris-(2-phenoxyphenyl)phosphine,tris-(2-p-methylphenoxyphenyl)phosphine,tris-(2-p-trifluoromethylphenoxyphenyl)phosphine,tris-(2-trifluoromethoxyphenyl)phosphine,tris-(2-methoxy-4-fluorophenyl)phosphine,tris-(2-methoxy-4-chlorophenyl)phosphine,tris-(2-methoxy-4-methylphenyl)phosphine,tris-(2,4-dimethoxyphenyl)phosphine,tris-(2,3-dihydrobenzofuran-7-yl)phosphine, trichroman-8-ylphosphine,tris-(2,3,4,5-tetrahydrobenzo[b]oxepin-9-yl)phosphine,tris-(2,3-dihydrobenzo[b][1,4]dioxin-5-yl)phosphinebis-(2-methoxyphenyl)phenylphosphine,bis-(2,4-dimethoxyphenyl)phenylphosphine,bis-(2-ethoxyphenyl)phenylphosphine,bis-(2-propoxyphenyl)phenylphosphine,bis-(2-i-propoxyphenyl)phenylphosphine,bis-(2-butoxyphenyl)phenylphosphine,bis-(2-sec-butoxyphenyl)phenylphosphine,bis-(2-t-butoxyphenyl)phenylphosphine,bis-(2-phenoxyphenyl)phenylphosphine,bis-(2-p-methylphenoxyphenyl)phenylphosphine,bis-(2-p-trifluoromethylphenoxyphenyl)phenylphosphine,bis-(2-trifluoromethoxyphenyl)phenylphosphine,bis-(2-methoxy-4-fluorophenyl)phenylphosphine,bis-(2-methoxy-4-chlorophenyl)phenylphosphine,bis-(2-methoxy-4-methylphenyl)phenylphosphine,bis-(2,3-dihydrobenzofuran-7-yl)phenylphosphine,bis(2-methoxyphenyl)(4-(trifluoromethyl)phenyl)phosphine,bis-(2,3-dihydrobenzo-[][1,4]dioxin-5-yl)phenylphosphine,dichroman-8-ylphenylphosphine, andbis-(2,3,4,5-tetrahydrobenzo[b]oxepin-9-yl)phenylphosphine.

Preferred suitable phosphines include, but are not limited to,tris-(2-methoxyphenyl)phosphine, tris-(2,4-dimethoxyphenyl)phosphine,bis-(2-methoxyphenyl)phenylphosphine,tris-(2-methoxy-4-fluorophenyl)phosphine, andtris-(2-methoxy-4-chlorophenyl)phosphine. More preferred suitablephosphines include, but are not limited to,tris-(2-methoxyphenyl)phosphine, bis-(2-methoxyphenyl)phenylphosphine,tris-(2-methoxy-4-fluorophenyl)phosphine, andtris-(2-methoxy-4-chlorophenyl)phosphine.

The process employs the phosphine ligand in an amount sufficient tostabilize the palladium catalyst in the reaction fluid and provide acatalyst efficiency sufficient to produce a product mixture comprising alinear product 1-RO-2,7-octadiene and a branched product3-RO-1,7-octadiene with a molar ratio of the linear product to thebranched product (L/B ratio) ≧25/1, preferably ≧26/1. The amount ofphosphine ligand provides an initial ligand to palladium molar ratio≧1.0. The initial phosphine ligand to palladium ratio is preferably ≧1.5to substantially stabilize the palladium catalyst in the reaction fluid.The phosphine ligand may at least partially decompose during the courseof the telomerization reaction. Preferably maintain a phosphine ligandto palladium ratio of ≧1.0 throughout the course of the telomerizationreaction, either by adding >one molar equivalent of the phosphineligand, or alternatively, by adding additional amount of the phosphineligand throughout the telomerization reaction. The initial phosphineligand to palladium ratio is advantageously less than (<) 50, andpreferably <40, so that the phosphine ligand provides sufficientstabilization to the palladium catalyst, as well as catalyst efficiencysufficient to produce the product mixture. Measure catalyst efficiencyby an average production rate of g of the linear product (LP) per gpalladium (Pd) per hour (hr) or gLP/gPd/hr. The catalyst efficiency ispreferably ≧150 gLP/gPd/hr, more preferably ≧200 gLP/gPd/hr, still morepreferably ≧400 gLP/gPd/hr, and still more preferably ≧1000 gLP/gPd/hr.

Using a preferred phosphine ligand, the process produces atelomerization product mixture comprising the linear (L) product1-RO-2,7-octadiene and the branched (B) product 3-RO-1,7-octadienepreferably with a catalyst efficiency ≧150 gLP/gPd/hr and a L/B ratio atleast 25/1.

The organic hydroxy compound can have one or more hydroxyl groups,except that the organic hydroxy compound is not glycerol. Examples ofsuitable organic hydroxy compounds methanol, ethanol, 1-propanol,2-propanol, 1-butanol, 2-butanol, t-butanol, 2-methylpropan-1-ol,2,2-dimethylpropan-1-ol, pentanols, hexanols, heptanols, octanols,decanols, dodecanols, tetradecanols, hexadecanols, octadecanols, phenol,ethylene glycol, propylene glycol, sorbitol, glucose, fructose, sucrose,and mixtures thereof.

The process optionally comprises additional steps to produce 1-octenefrom the telomerization product mixture. A typical process of convertingthe telomerization product mixture to 1-octene involves first subjectingthe telomerization product mixture under hydrogenation condition toreduce 1-RO-2,7-octadiene to 1-RO-octane, which can also be written asRO-1-octyl ether. Then either thermally or catalytically decompose theether to eliminate the RO— moiety and a beta hydrogen atom of the1-octyl moiety to regenerate the organic hydroxy compound ROH andproduce 1-octene. Advantageously, separate and reuse the organic hydroxycompound ROH in the butadiene telomerization reaction. WO92/10450(Bohley et al.), U.S. 2005/0038305 (Edwards), U.S. Pat. No. 7,030,286(Winger et al.), and U.S. Pat. No. 7,368,621 (Krissmann et al.)exemplify such 1-octene producing processes.

The present invention stems from a surprising discovery that catalystefficiency is inversely correlated to the molar concentration of theorganic hydroxy compound, preferably methanol, when using a phosphineligand as disclosed above.

The process employs the organic hydroxy compound in an amount such thata maximum concentration of the organic hydroxy compound in the reactionfluid during the course of the telomerization reaction is advantageouslyless than (<) 6.0 moles per liter (M), preferably <5.0 M, and still morepreferably <3.5 M, of the reaction fluid, and is advantageously >1.0 M,preferably >2.5 M, of the reaction fluid.

One can feed the organic hydroxy compound into the reaction fluid orzone batch-wise, continuously or a combination thereof. One preferablyfeeds each batch of organic hydroxy compound in an amount such that theorganic hydroxy compound has an initial concentration of >1.0 M ofreaction fluid, and a maximum concentration of <6.0 M of reaction fluidat any time of the reaction.

When employing continuous feeding, feed the organic hydroxy compoundinto the reaction fluid in a feed rate such that the concentration ofthe organic hydroxy compound is substantially maintained within theranges described hereinabove for a percentage of the reaction time. Thepercentage is advantageously >30%, preferably >40%, and morepreferably >50%, and is advantageously <100%, preferably <90%, and morepreferably <80% of the reaction time.

As a starting material, butadiene can be employed as pure butadiene oras a butadiene-containing C₄-hydrocarbon mixture. Other C₄-hydrocarbonsin such a C₄-hydrocarbon mixture include butenes and butanes. The otherC₄-hydrocarbons do not substantially influence conversion of thebutadiene present in the C₄-hydrocarbon mixture or selectivity towardsthe desired telomerization product. When the C₄-hydrocarbon mixturecontains acetylenes, optionally remove the acetylenes by, for example,selectively hydrogenating the C₄-hydrocarbon mixture before use becauseacetylenes may decrease palladium catalyst efficiency.

The process can employ any palladium catalyst or catalyst precursorknown in the art. The process advantageously employs palladium (Pd)metal, a Pd(II) compound, a Pd(0) complex, or a mixture thereof as thecatalyst or as a catalyst precursor that forms the catalyst under thereaction conditions in the process. Examples of suitable forms of Pdmetal include Pd powder, Pd black and Pd on carbon. Examples of suitablePd(II) compounds include Pd(II) chloride, Pd(II) bromide, Pd(II)acetate, Pd(II) formate, Pd(II) propionate, Pd(II) borate, Pd(II)citrate, Pd(II) hydroxide, Pd(II) octanoate, Pd(II) carbonate, Pd(II)sulfate, Pd(II) nitrate, Pd(II) acetylacetonate, Pd(II) alkyl-sulfonate,disodium palladium tetrachloride (Na₂PdCl₄), dipotassium palladiumtetrachloride (K₂PdCl₄), dichlorobis(benzonitrile)palladium,allylpalladium chloride, allylpalladium acetate, triallylpalladium, and1,5-cyclooctadienepalladium(II) chloride. When using Pd halides, anactivator needs to be added to the reaction. Preferred Pd(II) salts haveorganic anions, for example, Pd acetate or Pd acetylacetonate. Examplesof ligands in suitable palladium(0) complexes includeheteroatom-containing compounds, alkynes, alkenes and dienes. Examplesof heteroatom-containing compounds are phosphines, phosphites,phosphonites, phosphinites, amines, nitrites and pyridines. Specificexamples are bis(dibenzylideneacetone)palladium(0),tris(dibenzylideneacetone)dipalladium(0) andbis(1,5-cyclooctadiene)palladium. Preferably, the Pd catalyst orprecursor is a divalent Pd compound, for example, Pd(II)acetylacetonate.

The process employs a Pd catalyst concentration in the reaction fluidsufficient to produce a telomerization product mixture comprising1-RO-2,7-octadiene. Pd catalyst concentration depends on a particularphosphine ligand employed and other reaction conditions, such asbutadiene feed, either in pure form or in a C₄-hydrocarbon mixture.Calculate Pd catalyst concentration in parts per million by weight(ppmw) of Pd based on the weight of the reaction fluid. Theconcentration is advantageously >one (1) ppmw, preferably >two (2) ppmw,and more preferably >three (3) ppmw of Pd, and is advantageously <100ppmw, preferably <75 ppmw, and more preferably <50 ppmw of Pd.

Pd catalyst can be introduced as an active catalyst with the phosphineligand into the reaction fluid or a reaction zone. Advantageously,introduce a catalyst precursor, either separately or together with thephosphine ligand, into the reaction fluid to produce the active catalystwith the phosphine ligand under the reaction conditions.

When a Pd(II) compound is used as the catalyst precursor, it generallytakes a certain period of time to form the active catalyst under thereaction conditions. This time period, which depends on electronic andsteric properties of the phosphine ligand, is referred to as aninduction period. The induction period is generally >one (1) minute, but<two (2) hours. Optionally employ a catalyst promoter to shorten oressentially eliminate the induction period. Select a catalyst promoterfrom compounds having a pK_(b)>five (5), preferably >six (6), morepreferably >seven (7), and still more preferably >eight (8). Preferably,select a catalyst promoter from a group consisting of tertiary amines,alkali metal borohydrides, oxides, and compounds having a genericformula (R⁵O⁻)_(n)M^(n+), wherein R⁵ is hydrogen, a C₁-C₂₀-hydrocarbyl,or a substituted C₁-C₂₀-hydrocarbyl, M is an alkali metal, alkalineearth metal or quaternary ammonium, and n is one (1) or two (2).

The catalyst promoter, when used, is present in an amount that providesa molar ratio of catalyst promoter to Pd in the reaction fluid of ≧0.01,preferably ≧0.1, more preferably ≧0.5 up to <1000, preferably <800, andmore preferably <600.

The process optionally employs an organic solvent to carry out thetelomerization reaction. The process can employ any organic solvent solong as the solvent does not substantially interfere with the process,e.g. a solvent selected from a group consisting of C₄-C₁₂ alkanes,C₄-C₁₂ alkenes, C₆-C₁₂ arenes, C₄-C₁₂ ethers, C₅-C₁₂ tertiary amines,and mixtures thereof.

The organic solvent, when present, is employed in an amount such thatthe solvent comprises ≧20 wt %, preferably ≧30 wt %, and <80 wt %,preferably <70 wt % of the reaction fluid by weight, each wt % beingbased on reaction fluid weight.

Optionally, the process employs a carboxylic acid to stabilize the Pdcatalyst in solution, particularly during storage. Examples of suchcarboxylic acids include formic acid, acetic acid, propionic acid,butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid,pelargonic acid, capric acid, lauric acid, palmitic acid, stearic acid,benzoic acid, and benzilic acid. The process preferably employs acatalyst stabilizer in an amount sufficient to stabilize the Pdcatalyst. The amount provides preferably a molar ratio of the stabilizerto Pd ≧0.5, more preferably ≧one (1), and preferably <four (4), morepreferably <two (2).

Optionally, the process employs a radical inhibitor to prevent butadienepolymerization. Any known radical inhibitor is suitable so long as itdoes not substantially interfere with the telomerization reaction.Examples of suitable radical inhibitors include diethylhydroxyamine(DEHA), 2,6-di-tert-butyl-4-methylphenol (BHT), 4-tert-butylcatechol,hydroquinone, catechol, and phenol. When used, the radical inhibitor ispresent in an amount sufficient to provide a concentration of theradical inhibitor ≧one (1) ppmw, more preferably ≧five (5) ppmw, andpreferably <100 ppmw, more preferably <50 ppmw, based on the weight ofthe reaction fluid.

The Pd catalyst/precursor, phosphine ligand, catalyst stabilizer,catalyst promoter, and radical inhibitor, also referred to as “catalystcomponents”, can each be fed into the reaction fluid or zone separatelyor together as a mixture of >two catalyst components. Each catalystcomponent can be fed into the reaction fluid or zone either in itsoriginal form, or as a solution or as a slurry in the organic hydroxycompound, a solvent if employed, or a mixture thereof.

The process optionally includes preparation of a catalyst or catalystprecursor stock solution by dissolving a Pd compound/complex mentionedhereinabove, the phosphine ligand, and a catalyst stabilizer in theorganic hydroxy compound, in an organic solvent if employed, or in amixture of the organic hydroxy compound and an organic solvent. Thephosphine ligand, the catalyst stabilizer, or both can react with the Pdcompound to form one or more new Pd compounds/complexes comprising thephosphine ligand, the catalyst stabilizer, or both in the stocksolution.

The process can be carried out either in batch or continuously. Anybatch or continuous reactor can be employed. Examples of suitablereactors include stirred tank reactors, tubular reactors, andcombinations thereof.

The telomerization reaction is advantageously conducted under an inertatmosphere, such as nitrogen, argon, or helium, and at a reactiontemperature sufficient to produce the linear product 1-RO-2,7-octadieneat a catalyst efficiency within the ranges described hereinabove. Thereaction temperature is preferably >40° C., more preferably >50° C., andstill more preferably >60° C., and is preferably <120° C., morepreferably <110° C., and still more preferably <100° C. For a givencatalyst, catalyst efficiency increases with increasing temperaturewithin the ranges stated above.

The telomerization reaction is advantageously conducted in a sealedreactor at a pressure at least equal to the sum of vapor pressures ofreaction fluid components, such as butadiene, the organic hydroxycompound and the organic solvent if present, at a reaction temperaturewithin the ranges described hereinabove. The pressure can be increasedabove the sum of the vapor pressures by pressurizing an inert gas, suchas nitrogen, into the reactor. The pressure is preferably >0.1 megaPascal (mPa) (15 pounds per square inch (psi)), more preferably >0.2 mPa(29 psi), and still more preferably >0.4 mPa (58 psi), and is preferably<four (4) mPa (584 psi), more preferably <three (3) mPa (438 psi), andstill more preferably <two (2) mPa (292 psi).

The telomerization reaction is conducted for a reaction timesufficiently long to achieve a butadiene conversion of ≧50%, preferably≧70%, and more preferably ≧90%, when pure butadiene is employed; or abutadiene conversion of advantageously ≧90%, preferably ≧95%, and morepreferably ≧98%, when a butadiene-containing C₄-hydrocarbon mixture isemployed. The reaction time is preferably >one (1) minute, morepreferably >five (5) minutes, and still more preferably >10 minutes, andis preferably <24 hours, more preferably <18 hours, and still morepreferably <12 hours.

Depending on physical properties of the organic hydroxy compound,palladium catalyst, phosphine ligand, and optional solvent, one canisolate the desired product, e.g., 1-RO-2,7-octadiene or a mixturethereof with 3-RO-1,7-octadiene, by subjecting the reaction mixture toone or more distillation, extraction, or other well known separationtechniques, or a combination thereof, to separate unconverted reactantsand the optional solvent.

Telomerization products obtained via the above process find use asintermediates for a variety of applications, for example, in producingsurfactants, herbicides, saturated ethers, alcohols, acids, esters andolefins.

Solvent Preparation

Prepare anhydrous methylcyclohexane (MCH), tetrahydrofuran (THF) andmethanol (CH₃OH) purchased from Aldrich by flowing each solvent througha short column of activated alumina and a layer of silica gel to keepalumina fines from coming through the column in a glovebox undernitrogen. Treat dibutyl ether, purchased from Aldrich and used as aninternal standard for gas chromatography (GC) analysis, by firststirring it over sodium (Na)/potassium (K) alloy overnight and thenflowing it through a short column of activated alumina and a layer ofsilica gel in a glovebox under nitrogen.

Tris-(2,4-dimethoxyphenyl)phosphine (L2) preparation

Prepare a mixture by adding dropwise a THF (10 mL) solution ofphosphorus trichloride (PCl₃, 1.03 g, 7.50 mmol) into a stirring THFsolution of 2,4-dimethoxyphenylmagnesium bromide (50.0 mL of 0.5 Msolution in THF, 25.0 mmol) at −78° C. Stir the mixture at −78° C. for30 minutes, at room temperature for three (3) hours, and then at 50° C.overnight. Remove volatiles from the mixture to obtain a yellow residue,which is dissolved in acetonitrile and filtered to obtain a firstfiltrate. Remove volatiles from the first filtrate under vacuum toobtain a pale yellow solid. Add acetonitrile dropwise to the pale yellowsolid with agitation until essentially all the solid dissolves to obtaina solution. Filter the solution to remove any residual solid to obtain asecond filtrate. Place the second filtrate in a freezer (−10° C.)overnight to obtain a white crystalline solid. Isolate the crystallinesolid by decanting off the liquor and drying the crystalline solid undervacuum (1.07 g, 32.3%). ¹H NMR (CD₃CN): δ 3.75 (s, 3H), 3.84 (s, 3H),6.45-6.65 (m, 3H). ³¹P NMR (CD₃CN): δ −42.1.

Tris-(2-methoxy-4-fluorophenyl)phosphine (L4) preparation

Charge magnesium (Mg) turnings (1.18 g, 48.8 mmol) and five (5) mL THFunder nitrogen into a 3-neck round-bottom flask equipped with a refluxcondenser and heat the flask contents to 50° C. with a heating mantle.Add dropwise a solution of 2-bromo-5-fluoroanisol (5.00 g, 24.39 mmol)and 1,2-dibromoethane (0.51 g, 2.7 mmol) in THF (total volume of 15 mL)with stirring. Remove the heating mantle five (5) minutes aftercommencing the addition as the reaction heat becomes sufficient tomaintain the reaction temperature. After completing the addition inabout 50 minutes to yield a first mixture, reflux the first mixture foran additional 30 minutes to yield a brown solution. After allowing thebrown solution to cool to room temperature, separate the brown solutionfrom the unreacted Mg turnings by transferring the brown solution via acannula into a 100 mL round-bottom flask under nitrogen. Cool the brownsolution to −70° C. and add dropwise a solution of PCl₃ (1.038 g, 7.56mmol) in seven (7) mL THF with stirring over a period of 30 minutes toyield a second mixture. Heat the second mixture to 50° C. and stir thesecond mixture for two (2) hours at 50° C. After cooling flask contentsto room temperature and transferring the flask into a glovebox, filterthe second mixture and wash the filter with diethyl ether (20 mL) toobtain a filtrate. Remove volatiles from the filtrate under vacuum toyield a light brown solid. Dissolve this light brown solid in benzeneunder an inert nitrogen atmosphere to obtain a benzene solution and washthe benzene solution with deionized water (3×20 mL). Dry the organiclayer over MgSO₄ and then filter it to obtain a dry benzene solution.Remove benzene under vacuum to isolate an off-white solid, which isfurther purified by recrystallization from acetonitrile (1.60 g, 52.1%yield). ¹H NMR (C₆D₆): δ 2.99 (s, 3H), 6.30-6.33 (m, 1H), 6.49-6.52 (tof d, ³J_(HH)=8.2, 2.3, 1H), 6.82-6.86 (m, 1H). ³¹P NMR (C₆D₆,externally referenced using H₃PO₄): δ −38.9. ¹⁹F NMR (C6D6): −110.8 to−110.90 (m, 1F).

Tris-(2-methoxy-4-chlorophenyl)phosphine (L5) preparation

Replicate the procedure above for preparation of L4 with the followingexceptions: a) Mg turnings (0.604 g, 24.8 mmol) and two (2) mL THF; b)dropwise add a solution of 2-bromo-5-chloroanisol (5.0 g, 22.6 mmol) and1,2-dibromoethane (0.31 g, 1.65 mmol) in THF (total volume of 13 mL) toyield a first mixture; c) reflux the first mixture an additional 4hours, instead of 30 minutes; d) dropwise add a solution of PCl₃ (0.961g, 7.00 mmol) in THF (6 mL) to yield a second mixture; e) Reflux thesecond mixture for 3.5 hours, instead of heating at 50° C. for two (2)hours; and e) Isolate the product as a crystalline light brown solid(1.60 g, 50.2% yield). ¹H NMR (C₆D₆): δ 2.97 (s, 3H), 6.60-6.63 (dd,³J_(HH)=4.3 Hz, 1.7 Hz, 1H), 6.74-6.82 (m, 2H). ³¹P NMR (C₆D₆,externally referenced using H₃PO₄): δ −37.6.

Preparation of Bis(2-methoxyphenyl)(4-(trifluoromethyl)phenyl)phosphine(L6)

Stir 1-Bromo-4-(trifluoromethyl)benzene (0.593 g, 2.63 mmol) indiethylether (30 mL) while dropwise adding 0° C. as n-BuLi (2.63 mmol,1.32 mL of 2.0 M solution in cyclohexane). Allow this mixture to stirfor an additional hour, then add chlorobis(2-methoxyphenyl)phosphine(0.739 g, 2.63 mmol) as a solid. Continue stirring for four hours atroom temperature, then remove volatiles were removed and dissolveresidue benzene and filter to remove salts to yield a yellow residue.Dissolve the residue in a minimum amount of acetonitrile, filter thesolution, and place the solution in a glovebox freezer (−10° C.) toprecipitate crystals out of solution. Isolate the crystals by decantingoff the liquid and drying under vacuum. Replicate crystallization andcrystal isolation two more times to yield a white microcrystalline solid(0.419 g, 49.3%). ¹H NMR (C₆D₆): δ 3.16 (s, 6H), 6.47-6.52 (m, 2H),6.71-6.77 (m, 2H), 6.90-6.95 (m, 2H), 7.08-7.15 (m, 2H), 7.21-7.25 (m,2H), 7.31-7.37 (m, 2H). ¹³C NMR (C₆D₆): 55.2, 110.6, 121.4, 125.1 (m),130.7, 134.23, 134.25, 134.4, 134.7, 143.4, 161.8 (d, 15.7 Hz). ³¹P NMR(C₆D₆, externally referenced using H₃PO₄): δ −24.6. ¹⁹F NMR (C₆D₆,externally referenced using CCl₃F): −62.7.

TABLE 1 Ligands employed to illustrate some embodiments of the inventionNo. Name Source Comments L1 Tris-(2-methoxyphenyl)- Strem Having 3ortho-methoxy phosphine substituted phenyl rings. L2Tris-(2,4-dimethoxyphenyl)- Prepared Having 3 ortho- and phosphinepara-methoxy substituted phenyl rings. L3 Bis-(2- Strem Having 2ortho-methoxy methoxyphenyl)phenyl- substituted phenyl rings. phosphineL4 Tris-(2-methoxy-4- Prepared Having 3 ortho-methoxy andfluorophenyl)-phosphine para-fluoro substituted phenyl rings. L5Tris-(2-methoxy-4- Prepared Having 3 ortho-methoxy andchlorophenyl)-phosphine para-chloro substituted phenyl rings L6Bis(2-methoxyphenyl)(4- Prepared Having 2 ortho-methoxy (trifluoro-substituted phenyl rings and methyl)phenyl)phosphine apara-trifluoromethyl substituted phenyl ring.

Catalyst Stock Solution Preparation

Prepare a catalyst stock solution using L1 according to the followingprocedure:

Dissolve Pd(II) acetylacetonate (Pd(acac)₂, 0.0294 g, 0.097 mmoles,Aldrich: 05615EH), L1 (0.0642 g, 0.193 mmoles) and acetic acid (AcOH,0.097 mmoles, 0.50 mL of 0.193 M AcOH in CH₃OH) in MeOH to obtain asolution having a total volume of 50.0 mL. Stir this solution forapproximately 30 minutes to obtain a Pd-L1 catalyst stock solutionhaving 1.93 mmol/liter of palladium and 3.86 mmol/liter of L1. Aceticacid is used to stabilize the catalyst stock solution during storage.

Prepare catalyst stock solutions using each of the phosphine ligands:L2-L7 according to the above procedure. Each Pd-L catalyst stocksolution has the same concentrations of Pd and the ligand as in thePd-L1 catalyst stock solution.

Prepare a catalyst stock solution according to the procedure hereinaboveusing each of the comparative ligands (CL) shown in Table 2. Each Pd-CLcatalyst stock solution has the same concentrations of Pd and the ligandas in the Pd-L1 catalyst stock solution.

TABLE 2 Comparative ligands No. Name Source Comments CL1Triphenylphosphine Aldrich None of the phenyl rings is substituted CL22-Methoxyphenyldiphenyl- Aldrich Having only one phosphine ortho-methoxysubstituted phenyl ring. CL3 Tris-(4-methoxyphenyl)- Aldrich No orthomethoxy phosphine group on any of the phenyl rings. CL4Tris-(2,4,6-trimethoxyphenyl)- Strem Methoxy groups on phosphine allortho and para positions of all 3 phenyl rings.

Preparation of Stock Solutions of a Catalyst Promoter (Sodium Methoxide(NaOMe)), a Butadiene Polymerization Inhibitor (diethylhydroxyamine(DEHA)), and H₂O

Prepare NaOMe and DEHA stock solutions in methanol using anhydroussodium methoxide (NaOMe) and DEHA from Aldrich as received, and a H₂Ostock solution in methanol using degassed and deionized H₂O. Prepare,store and dispense all stock solutions under a nitrogen atmosphere. Theconcentrations of DEHA, H₂O, and NaOMe, in their respective stocksolutions in methanol are shown in Table 3.

TABLE 3 Concentrations of the minor component in each stock solutionDEHA in H₂O in NaOMe in Stock solution methanol methanol methanolConcentration of solute (mM) 4.47 3.83 19.3

General Procedures for Reactor Loading

In a glovebox, syringe butylether, MeOH, methylcyclohexane, a catalyststock solution, the DEHA/MeOH stock solution, the H₂O/MeOH stocksolution and the NaOMe stock solution, in this order, into an openFisher-Porter brand glass reactor that has a maximum working pressure of200 psi (1.4 mPa). Adding water to the reaction solutions simulateslarge scale or commercial operations where solvents and reactantsgenerally contain trace amounts of water.

Close the reactor tightly with a reactor head equipped with a pressuregauge, a 150 psi (1.0 mPa) pressure relief valve, and a valve cappedwith a septum port. Inject 5.5 mL of 1,3-butadiene, using a gas-tightsyringe, into the reactor via the septum with the needle placed justbelow the surface of the liquid. Determine the injected amount of1,3-butadiene by weighing the syringe before and after the injection.

EXAMPLES (Ex) 1-4

Load four Fisher-Porter brand glass reactors using the Pd-L1 catalyststock solution according to the general procedure described above withthe volumes of the stock solutions and other components in eachreactor/example shown in Table 4.

TABLE 4 Solution and components added into reactors for Examples 1-4.Example/Reactor NO. 1 2 3 4 Dibutyl ether (mL) 5.0 5.0 5.0 5.0 Make-upMeOH (mL) 1.0 0.0 1.7 9.5 Make-up MCH (mL) 12.1 11.1 9.4 1.6 Pd-L1 stocksolution (mL) 1.0 1.0 1.0 1.0 DEHA stock solution (mL) 0.0 1.0 1.0 1.0H₂O stock solution (mL) 0.0 1.0 1.0 1.0 NaOMe stock solution (mL) 0.50.5 0.5 0.5 1,3-Butadiene (mL) 5.5 5.5 5.5 5.5 1,3-Butadiene (g) 3.4 3.43.4 3.4 Final Volume (mL) 25.1 25.1 25.1 25.1

Table 5 below shows the initial concentrations of the added componentsin each Ex/reactor, either in moles/liter (M), or parts per million byweight (ppmw) based on the weight of the solution, molar ratios of Pd/L1and NaOMe/Pd, and the maximum grams of 1-methoxy-2,7-octadiene that canbe theoretically produced based on the amount of butadiene charged intoeach reactor per gram palladium. The acetic acid or its reaction productwith Pd(acac)₂ in the catalyst stock solution may reduce the NaOMe/Pdmolar ratio by up to one (1).

TABLE 5 The initial concentrations of the added components in Ex 1-4Example/Reactor NO. 1 2 3 4 Dibutyl ether (M) 1.2 1.2 1.2 1.2 MeOH (M)2.5 3.4 5.1 12.7 MCH (M) 3.8 3.5 2.9 0.5 1,3-Butadiene (M) 2.5 2.5 2.52.5 Pd (ppmw) 11 11 11 11 L/Pd (mol/mol) 2 2 2 2 NaOMe/Pd (mol/mol) 5 55 5 DEHA (ppmw) 0 20 20 20 H₂O (ppmw) 0 4 4 4 Max. g MOD-1/g Pd 2175021750 21750 21750

Carry out Ex 1-4 by placing the reactors into oil baths preheated to 90°C. and stirring the reactor contents for two (2) hours. Thereafter,remove the reactors from the oil baths, allow the reactors to cool toroom temperature, vent the reactors by opening the pressure reliefvalves, and then opening the reactors to obtain product solutions.

Ex 5-8

Replicate Ex 1-4, except that the reaction times are four (4) hours.

Ex 9 and 10

Replicate Ex 3 and 4 using the catalyst stock solution prepared usingL2.

Ex 10-22

Replicate Ex 3, 4 and 8 using the catalyst stock solutions preparedusing L3, L4, L5 and L6.

Sample Analysis and Data Acquisition by Gas Chromatography

Analyze the product solutions on a HP 6890 gas chromatography (GC) usinga low thermal mass column (LTM-DB-1701) and the following method:

-   Column: LTM-DB-1701; Length: 30 m; Diameter: 320 μm; Film thickness:    1.0 μm; Mode: constant flow; Initial column flow: 1.4 mL/min-   Front inlet: Mode: split; Initial Temp: 250° C.; Pressure: 7.19 psi;    Split ratio: 50:1; carrier gas: H₂.-   Detector: Flame ionization detector (FID); Temp: 300° C.; H₂ flow:    40.0 mL/min; Air flow: 450.0 mL/min Make up gas: Nitrogen.-   Ovens: HP 6890 oven:    -   Isothermal at 250° C.    -   LTM column oven:    -   Initial Temp: 65° C. and hold for 110 seconds;    -   Ramp at 300° C./min to 120° C. and hold for 100 seconds;    -   Ramp at 300° C./min to 250° C. and hold for 233 seconds.    -   Total run time: 8.0 minutes.    -   Column cooling time to 65° C.: less than 2 minutes.

Prepare a standard sample by using known amounts (grams) of eight (8) GCobservable components, methanol, butadiene, dibutyl ether (GC InternalStandard (IS)), 1-methoxy-2,7-octadiene (MOD-1), 3-methoxy-1,7-octadiene(MOD-3), octatrienes, octadienes and vinylcyclohexene. Run the standardsample on the GC to determine retention times and response factors ofthe eight (8) components. Calculate a response factor (RF(i)) for eachcomponent/peak (i) by the equation:RF(i)=[(peak(i)-grams)/(peak(i)-area)]/[(IS-grams/IS-area)]wherein i=1 through 8.

Prepare a GC sample by taking a one (1) milliliter of a product solutionwithout any dilution. Obtain a chromatogram from the sample using the GCmethod described above. Use the peak area table of the chromatogram, theRFs of the components (peaks) and the amount of dibutyl ether in theproduct solution to carry out the following calculations:Grams of component(i)=(RF(i)*peak-area(i))/(IS-grams/IS-area);Moles of the component(i)=(Grams of the component(i))/(molecular weightof the component(i));Moles of all product=Sum of moles of MOD-1, MOD-3, octatrienes,octadienes and vinylcyclohexene.Conv(mol %)=(moles of butadiene converted)/(moles of butadiene fed intothe reactor);MOD-1(mol %)=(moles of MOD-1)/(Moles of all products);MOD-3(mol %)=(moles of MOD-3)/(Moles of all products);MOD-1/MOD-3 molar(L/B) ratio=(moles of MOD-1)/(moles of MOD-3);Catalyst efficiency=(grams of MOD-1)/(grams of Pd)/(hours of reactiontime).

Table 6 hereinbelow shows the results from Ex 1-22 calculated accordingto the above equations.

TABLE 6 Results from examples 1-28 Ex Ligand [MeOH] RXT Conv MOD-1 MOD-3L/B Catalyst No. No. (M) (far) (mol %) (mol %) (mol %) ratio efficiency¹1 L1 2.5 2 33.4 94.4 3.5 27 3477 2 L1 3.5 2 28.3 94.0 3.4 28 2943 3 L15.1 2 30.3 94.2 3.3 29 3117 4 L1 12.7 2 5.8 88.4 2.7 33 559 5 L1 2.5 433.4 93.5 3.5 27 1721 6 L1 3.5 4 28.1 93.8 3.4 28 1460 7 L1 5.1 4 30.194.0 3.3 29 1545 8 L1 12.7 4 4.1 86.1 2.6 33 194 9 L2 5.1 2 2.6 85.4 3.128 245 10 L2 12.7 2 1.8 78.7 2.7 30 154 11 L3 5.1 2 65.5 93.9 3.6 266861 12 L3 12.7 2 22.1 91.8 3.1 30 2302 13 L3 12.7 4 21.5 91.5 3.1 301065 14 L4 5.1 2 47.4 94.7 3.3 29 5022 15 L4 12.7 2 15.8 93.7 3.0 321626 16 L4 12.7 4 19.5 94.1 2.9 32 1004 17 L5 5.1 2 35.5 93.5 3.7 263757 18 L5 12.7 2 31.2 95.4 3.0 32 3312 19 L5 12.7 4 29.8 95.3 3.0 321575 20 L6 5.1 2 72.5 94.2 3.4 28 7498 21 L6 12.7 2 76.6 95.0 3.4 287777 22 L6 12.7 4 84.6 94.7 3.4 28 4299 ¹Catalyst efficiency = (grams ofMOD-1)/(grams of Pd)/(hours of reaction time).

Data in Table 6 above show that each catalyst of the phosphine ligand L1through L6 produces, under the reaction conditions describedhereinabove, a product mixture with a catalyst efficiency at least 150 gof MOD-1 per g Pd per hour and a MOD-1 to MOD-3 molar ratio of 25/1 orhigher. Furthermore, these palladium catalysts are more efficient whenthe initial concentration of methanol in the reaction fluid is 5.1mol/liter than when it is 12.7 mol/liter.

Ex 23 and 24

Replicate Ex 4 (Pd-L1 catalyst stock solution, methanol concentration of12.7 moles/liter and reaction time of 2 hours), except that additionalamounts of L1 are added into the reaction solutions of Ex 23 and 24 toprovide L1/Pd molar ratios of 5 and 30, respectively. Obtain GC datafrom each example and carry out calculations according to the equationsdescribed hereinabove. Table 7 shows the calculated results. The resultsfrom example 4 are reproduced here for easy comparison.

TABLE 7 Results from examples 20 and 21. Ex L1/Pd Conv MOD-1 MOD-3 L/BCatalyst No. Mol/mol (mol %) (mol %) (mol %) ratio efficiency¹ 4 2 5.888.4 2.7 33 559 23 5 7.2 90.3 2.6 35 708 24 30 24.3 94.4 3.0 32 2546¹Catalyst efficiency = (grams of MOD-1)/(grams of Pd)/(hours of reactiontime).

The data in Table 7 show that higher L1/Pd ratios (e.g., 30) lead tohigher butadiene conversion, which can be interpreted as a result ofstabilization of the Pd catalyst for a longer period of time by theadditional amounts of the L1. The reaction conditions of all threeexamples are essentially the same except the L1/Pd ratios.

COMPARATIVE EXAMPLES CEx

Carry out butadiene telomerization reactions using the catalyst stocksolutions of the four (4) comparative ligands shown in Table 2hereinabove.

CEx 1-6

Replicate Ex 2, 3, 4, 6, 7 and 8 hereinabove using the Pd-CL1 catalyststock solution.

CEx 7-9

Replicate Ex 3, 4, and 8 hereinabove using the Pd-CL2 catalyst stocksolution.

CEx 10-12

Replicate Ex 3, 4, and 8 hereinabove using the Pd-CL3 catalyst stocksolution.

CEx 13 and 14

Replicate Ex 3 and 4 hereinabove using the Pd-CL4 catalyst stocksolution.

Obtain GC data from each comparative example and carry out calculationsaccording to the equations described hereinabove. Table 8 shows thecalculated results from CEx 1-14.

TABLE 8 CEx using comparative ligands CEx Ligand [MeOH] RXT Conv MOD-1MOD-3 L/B Catalyst No. No. (M) (far) (mol %) (mol %) (mol %) ratioefficiency¹ 1 CL1 3.7 2 31.7 76.5 5.4 14 2633 2 CL1 5.1 2 39.1 73.5 4.317 3032 3 CL1 12.7 2 78.7 89.2 4.6 20 7370 4 CL1 3.7 4 42.3 72.3 4.8 151650 5 CL1 5.1 4 63.6 77.9 5.3 15 2660 6 CL1 12.7 4 83.2 89.6 4.5 204063 7 CL2 5.1 2 65.6 87.7 4.7 19 6354 8 CL2 12.7 2 55.7 93.6 3.9 245707 9 CL2 12.7 4 65.6 93.6 3.9 24 3363 10 CL3 5.1 2 80.1 89.2 5.0 187619 11 CL3 12.7 2 76.4 90.5 4.5 20 7595 12 CL3 12.7 4 87.8 90.7 4.5 204447 CE13 CL4 5.1 2 1.0 9.5 0.2 47 11 CE14 CL4 12.7 2 0.5 6.0 0.8 8 3¹Catalyst efficiency = (grams of MOD-1)/(grams of Pd)/(hours of reactiontime).

The data in Table 8 show that the Pd catalysts of CL1-CL3 produceMOD-1/MOD-3 molar ratios of 24/1 or less, while Pd catalysts of CL4 hasvery low catalyst efficiency and produces MOD-1/MOD-3 molar ratioshighly dependent on reaction conditions.

What is claimed is:
 1. An improved process for telomerizing butadiene,the process comprising contacting butadiene and an organic hydroxycompound represented by formula ROH (I), wherein R is a substituted orunsubstituted C₁-C₂₀-hydrocarbyl and the organic hydroxy compound is notglycerol, in a reaction fluid in the presence of a palladium catalystand a phosphine ligand, the improvement comprising, a) the phosphineligand being selected from a group represented by formula (II):

wherein: R¹, R², R³ and R⁴ are each independently selected from thegroup consisting of hydrogen, halogen, substituted and unsubstitutedC₁-C₂₀-hydrocarbyls, and substituted and unsubstitutedC₁-C₂₀-hydrocarbyloxyls, provided that at least two R¹ moieties areindependently selected from substituted and unsubstitutedC₁-C₂₀-hydrocarbyloxyls and that the phosphine ligand has a total of two(2), three (3), four (4), five (5), or six (6) substituted orunsubstituted C₁-C₂₀-hydrocarbyloxyls; wherein optionally on each phenylring, R¹ is bonded to R² to form a 5- to 7-membered ring, R² is bondedto R³ to form a 5- to 7-membered ring, or R³ is bonded to R⁴ to form a5- to 7-membered ring; and b) which contacting occurs in a reactionfluid, which reaction fluid comprises the butadiene, the organic hydroxycompound, the palladium catalyst, and the phosphine ligand, underconditions and for a reaction time sufficient to yield a product mixturecomprising a linear product 1-RO-2,7-octadiene and a branched product3-RO-1,7-octadiene with a linear product to branched product molar ratioof greater than 25/1 and a catalyst efficiency at least 150 grams of thelinear product per gram palladium per hour, wherein R is as definedabove.
 2. The process of claim 1, wherein the phosphine ligand isselected from tris-(2-methoxyphenyl)phosphine,tris-(2,4-dimethoxyphenyl)phosphine,bis-(2-methoxyphenyl)phenylphosphine,tris-(2-methoxy-4-fluorophenyl)phosphine, andtris-(2-methoxy-4-chlorophenyl)phosphine.
 3. The process of claim 1,wherein the organic hydroxy compound is fed into the reaction fluid inan amount sufficient to provide a concentration of the organic hydroxycompound in a range from 1.0 to 6.0 moles per liter of the reactionfluid.
 4. The process of any one of claim 1, wherein the reaction fluidcomprises from 1 to 100 parts per million palladium by weight based onthe weight of the reaction fluid.
 5. The process of any one of claim 1,wherein the reaction fluid comprises from 1.0 to 50 moles of thephosphine ligand per mole of palladium.
 6. The process of any one ofclaim 1, further comprising a catalyst promoter having a pK_(b) ofgreater than 5, the catalyst promoter being selected from a groupconsisting of tertiary amines, alkali metal borohydrides, oxides, andcompounds having a generic formula (R⁵O⁻)_(n)M^(n+), wherein R⁵ ishydrogen, or a substituted or unsubstituted C₁₋₂₀ hydrocarbyl, M is analkali metal, alkaline earth metal or quaternary ammonium, and n is 1 or2.
 7. The process of claim 6, wherein the catalyst promoter is employedin an amount from 0.01 to 1000 moles per mole of palladium.
 8. Theprocess of any one of claim 1, further comprising an organic solvent inan amount from 20% by weight to 80% by weight based on the weight of thereaction fluid.
 9. The process of claim 8, wherein the organic solventis selected from the group consisting of C₄-C₁₂ alkanes, C₄-C₁₂ alkenes,C₆-C₁₂ arenes, C₄-C₁₂ ethers, C₅-C₁₂ tertiary amines, and mixturesthereof.
 10. The process of claim 1, further comprising the steps of:(a) hydrogenating the product mixture under hydrogenation conditionseffective to produce hydrogenation products comprising 1-RO-octane; and(b) eliminating the RO— group from the hydrogenation products underelimination conditions effective to produce elimination productscomprising 1-octene.